Nanostructured alumina particles synthesized by the Spray Pyrolysis method: microstructural and morphological analyses

Ultrafine particles or nanoparticles (ranging from a few nanometers to 100 nm) are of considerable interest for a wide variety of applications, ranking from catalyst to luminescence ceramics, due to their unique and improved properties primarily determined by size, composition and structure. This study presents the preparation and characterization of nanostructured spherical alumina particles by the Spray Pyrolysis method for the application in reinforcements of metal-matrix composites (MMCs). Synthesis procedure includes aerosol formation ultrasonically from alumina nitrate water solution and its decomposition into a tubular flow reactor at 700 °C. The obtained particles are spherical, smooth, amorphous and in non-agglomerated state. Microstructural and morphological analyses were carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM/EDS) and analytical and high resolution transmission electron microscopy (TEM/HRTEM).     

Boron-doped mullite derived from single-phase gels

Mullite with low dielectric constant and high transparency in infrared and microwave range has potential applications in communication industry. To improve the above properties of mullite, boron-doped mullite single-phase gels with a constant molar ratio of Al/Si = 3/1 and various B/Al ratios (B/Al = 0–0.4/3) were prepared in this study by slow hydrolysis of aluminum nitrate, boric acid and tetraethoxysilane. It was found that boron reduces the mullite formation temperature and suppresses spinel formation. The cell unit lattice parameters and cell volume in boron-doped mullite generally decrease with the increase of boron amount. The SEM observation shows that a small amount of boron reduces the grain sizes of mullite sintered bodies while a large amount of boron facilitates the formation of elongated grains and the amorphous glass phase. Boron decreases the transmittance of mullite ceramic and produces additional intensive absorption bond at 3.9 μm and also reduces the dielectric constants in the frequent range of 1 M–1 GHz.     

Influence of synthesis conditions on the properties of Y2O3–MgO nanopowders and sintered nanocomposites

In this study, a citrate–nitrate combustion method was applied to synthesize composite Y₂O₃–MgO nanopowders. In order to optimize the synthesis condition to support sufficient combustion, the molar ratio of citric acid to nitrate (c/n molar ratio) used in the reaction mixtures was varied between 0.17 and 0.34. Nanopowders with an average particle size of 17 nm were achieved. The properties of these nanopowders indicated that the higher molar ratios decreased the unreacted organic components and increased the amount of carbide on the surface of the oxides, which helped to inhibit the formation of carbonate groups. The amount of carbonate groups was reduced with the increasing c/n molar ratio. Y₂O₃–MgO nanocomposites fabricated through hot-isostatic-pressing sintering showed a uniform distribution of Y₂O₃ and MgO grains, which had an average size of ∼180 nm. In addition, the absorption peaks at 1410 and 1511 cm⁻¹ disappeared until the c/n molar ratio reached 0.28. A high average infrared transmittance of 83% in the range of 4000–1667 cm⁻¹ (2.5–6 μm) was obtained in the nanocomposites.     

Synthesis and mechanical properties of porous alumina from anisotropic alumina particles

A porous alumina body was synthesized from anisotropic alumina particles (platelets). The uniaxial pressure in fabricating the green compact body had an influence on the relative density of the alumina body after heating. When green compacts, which had been uniaxially pressed at 1 and 3 MPa, were heated at 1400 °C for 1 h, the relative densities of the resulting alumina bodies were 25.0% and 35.5%, respectively. The compressive strength of compacts that were uniaxially pressed at 1 and 3 MPa were 0.8 and 4.3 MPa, respectively. In an attempt to increase the compressive strength of these porous alumina bodies, aluminum nitrate and magnesium nitrate solution treatments were performed, followed by reheating to 1400 °C for 1 h. When a 0.5 mol/l aluminum nitrate solution was used, the compressive strength of the porous alumina body uniaxially pressed at 1 MPa changed from 0.8 MPa (without solution treatment) to 1.5 MPa. Furthermore, when 0.1 mol/l magnesium nitrate solution was used, the compressive strength of the porous alumina increased to 1.7 MPa. Thus, solution treatment of the porous alumina body had a strong positive effect on its mechanical strength.     

Synthesis of lutetium aluminum garnet powders by nitrate–citrate sol–gel combustion process

Polycrystalline lutetium aluminum garnet (Lu₃Al₅O₁₂) powders were prepared by a simple sol–gel combustion method using aluminum nitrate, lutetium oxide and citric acid as the starting materials. The XRD results showed that the amorphous precursor converted directly to pure LuAG at 900 °C. The TEM investigations revealed that the synthesized LuAG powders are nano-sized with an average particle size 20–30 nm.     

Dependence of zinc aluminate microscopic structure on its synthesis

Alumina doped with zinc oxide was synthesized by sol–gel method in alcohol solution. Hybrid oxides of aluminum and zinc were prepared from various aluminum precursors (aluminum sec-butoxide, aluminum nitrate, and aluminum isopropoxide) and zinc acetate solution with ethylacetoacetate and nitric acid as a chelating agent and catalyst, respectively. Types and molar ratio of the precursor to the chelating agent and acidic catalyst were found to remarkably affect the formation of transparent sol of aluminium–zinc sol composite. With relatively low temperature of 50 °C, the suitable molar ratio of aluminum sec-butoxide to ethylacetoacetate to nitric acid for preparing the homogeneous sol was 1:0.40:0.86. Furthermore, the calcination at elevated temperature higher than 400 °C would be essential for preparing ZnAl₂O₄ with the face centered cubic microstructure. The primary crystalline size of the synthesized zinc aluminate nanostructure was approximately 20 nm with lattice spacing of 0.55 nm.     

Processing of low-density alumina foam

A novel method for synthesizing low-density alumina foam has been developed. The alumina foam with 98.5% porosity was synthesized by an unconventional route from an aqueous aluminum nitrate–sucrose solution. The resin formed by heating this solution underwent foaming and set into solid green foam, which was sintered at 1873 K. The thermogram of the green foam showed mass loss in four stages. The foam exhibited interconnected porous network with window size in the range 103–226 and 167–311 μm for foams sintered at 1223 and 1873 K, respectively. The alumina foam sintered at 1223 K exhibited gamma phase and that sintered at 1873 K exhibited alpha phase.     

The effect of ceramic nanoparticles on tribological properties of alumina sol–gel thin coatings

Thin alumina coatings containing zirconia or alumina nanoparticles having diameter of ～20–30 nm were deposited by the sol–gel dip-coating process on silicon wafers. The mass content of nanoparticles in the alumina coating was fixed at 15% in relation to the theoretical mass of alumina matrix resulted from the amount of the applied precursor. Atomic force microscopy (AFM) was used to image the surface topography of as-made coatings and find out the wear level after frictional tests. Tribological tests were performed with the use of a microtribometer operating in the load range of 30–100 mN. It was found that the presence of α-alumina (corundum) or zirconia nanoparticles enhances the tribological performance of alumina layers annealed at 100 °C by decreasing the average wear rate by 20% and 63% for zirconia and corundum nanoparticles, respectively. No wear was observed for samples containing both types of nanoparticles annealed at 500 °C.     

Preparation of nanocrystalline SrTiO3 powder by sol–gel combustion method

In this research a sol–gel combustion route has been presented to synthesize strontium titanate (SrTiO₃:ST) nanocrystalline, using citric acid as fuel. The synthesis procedure was optimized by systematically varying the molar ratios of total metal nitrate to citric acid (MN:CA) from 1:1 to 1:3. The effect was investigated through XRD, SEM and TEM analysis. Analysis of XRD spectrum shows the complete of SrTiO₃ nanocrystalline, however, a minor phase of SrCO₃ impurity was found. Hence, an acid treatment process, with 1 mol/l HNO₃ solution and deionized water, was applied to remove the impurity. The results show that the appropriate condition to prepare the single phase nanocrystalline SrTiO₃ powders is MN:CA molar ratio of 1:3, coupled with an acid treatment process and at the lower calcination temperature of 500 °C. The particle size of powders was in nanometer ranges. The average crystallite size calculated from FWHM was about 23 nm. Morphology of powders was identified by SEM analysis. However, TEM estimated the average particle size about 7.5 nm after applying an acid treatment technique at 600 °C.     

The effect of the ethylene glycol to metal nitrate molar ratio on the phase evolution,morphology and magnetic properties of single phase BiFeO3 nanoparticles

In this work, single phase BiFeO₃ nanoparticles have been synthesized by thermal decomposition of a glyoxylate complex achieved by the redox reaction between ethylene glycol and nitrate anions. The effects of different molar ratios of ethylene glycol to metal nitrate anions on the phase evolution, morphology and magnetic properties were investigated by infrared spectroscopy, thermal analysis, X-ray diffraction, electron microscopy and vibrating sample magnetometry methods. The single phase bismuth ferrite nanoparticles synthesized with the ethylene glycol to nitrate anions molar ratio of 5 showed the weak ferromagnetism behavior with saturation magnetization of 1.3 emu/g, due to the size confinement effect. Furthermore, the BiFeO₃ nanoparticles were used for the degradation of methylene blue (MB) as a typical dye pollutant under direct sunlight irradiation.     

Microwave sintering of mullite–cordierite precursors prepared from solution combustion synthesis

Mullite–cordierite composite was synthesized using the solution combustion synthesis method and glycine as a fuel and aluminum nitrate, magnesium nitrate and colloidal silica as the reagents. The effect of fuel to oxidizer ratio on the combustion behavior, as well as chemical composition and morphology of the formed powders was investigated. All synthesized powders were amorphous with submicron particle size. It was found that the change of fuel to oxidizer ratio had no effect on synthesis of this composite without heat treatment. The smallest particle size of composite powder was obtained as 302 nm for ratio less than 1 (rich of fuel). Mullite, cordierite and spinel were detected after microwave heating at 1200 and 1400 °C. Mullite and cordierite were detected as the only crystalline phases when the stoichiometric ratio of fuel to oxidizer was chosen and this composite obtained the highest density of 2.61 g/cm³.     

Synthesis of nano-sized indium oxide (In2O3) powder by a polymer solution route

Indium oxide (In₂O₃) is a n-type semiconductor with various applications in thin film coatings, on the basis of its optical properties, and in gas sensing equipment, due to its high sensitivity to various oxides such as CO_x and NO_x. In this study, a synthesis process for obtaining In₂O₃ nanoparticles is examined. The precursor used is indium nitrate hydrate (InN₃O₉·H₂O) because of its high solubility in water. By dissolving the nitrate salt in a PVA (polyvinyl alcohol) solution, the precursor is dispersed homogeneously, which reduces the agglomeration of the resulting powder. Calcination at a low temperature of 200–250 °C burns out the organic materials of the PVA with NO_x gas emission and allows the oxidation of the indium, resulting in indium oxide nanoparticles. The influence of the PVA solution characteristics and the heat treatment temperature on the powder morphology and size was analyzed by using SEM, TEM, XRD, TGA/DSC, and four point BET for a specific surface area analysis. The measured specific surface area varies from 3 m²/g to 76 m²/g depending on the calcination temperature, and the particle size of the synthesized powders is under 10 nm for the samples heat treated at 300 °C.     

Preparation of alumina foams by the thermo-foaming of powder dispersions in molten sucrose

The alumina powder disperses in molten sucrose due to the hydrophilic interaction between the particle surface and sucrose hydroxyls. The thermo-foaming of the dispersions is due to the bubbles created by the water vapour produced by the OH condensation at 150 °C which are stabilized by the alumina particles adsorbed on the gas–liquid interface as well as the increase in viscosity. The foaming time, the foam setting time and the foam volume depend on the alumina powder to sucrose weight ratio. The alumina foams have interconnected cellular microstructure and the cells are having a near spherical morphology. The porosity (97.84–93.29 vol.%.) decreased and the average cell size (0.54–1.2 mm) increased with the increase in alumina powder to sucrose weight ratio (0.4–1.4). The alumina foams with density in the range of 0.239–0.267 g/cc showed compressive strength in the range of 1.02–1.47 MPa.     

Preparation of stable cross-linked enzyme aggregates (CLEAs) of NADH-dependent nitrate reductase and its use for silver nanoparticle synthesis from silver nitrate

The NADH-dependent nitrate reductase from Fusarium oxysporum cell extract was directly immobilized as cross linked enzyme aggregates (CLEAs) and investigated for the synthesis of silver nanoparticles by a reduction of silver nitrate. The effects of precipitant type and cross-linking on activity recovery of enzyme in CLEAs were studied. After aggregation of enzyme with ammonium sulfate followed by cross-linking formed aggregates for 4 h with 8 mM glutaraldehyde, 93% activity recovery was achieved in CLEAs with enhanced thermal stability at 50 °C and 40 °C. Scanning electron microscopy analysis showed that immobilized NADH-dependent nitrate reductase was of spherical structure. CLEAs showed 90% catalytic yield even after 4 cycles of repeated use in silver nanoparticle synthesis at pH 7.2 and temperature 35 °C.     

Low temperature synthesis of ultrafine non vermicular α-alumina from aerosol decomposition of aluminum nitrates salts

In this paper, spherical, smooth and unagglomerated ultrafine amorphous powder particles were prepared by ultrasonic spray pyrolysis (USP) of easy-handling aqueous aluminum nitrate salts increasing the precursor solute concentration to 0.5 mol L^?1 and reducing the pyrolysis temperature to 700 °C. The transformation of the USP alumina powders into α-Al₂O₃ was studied using combination of X-ray diffraction, electron microscopy, infrared spectroscopy, BET surface area, thermogravimetry and differential thermal analysis. A downward shift of the onset temperature of α-phase transformation to 900 °C has been detected using a larger precursor solution concentration and performing a milling before calcination due to an increase in the surface density of defects, in surface area and in anisotropic particle shape. Additional post-milling of the low calcined powders allowed the preparation of agglomerate-free pure ultrafine α-Al₂O₃ powder particles (～100 nm, 28 m² g^?1), free of vermicular microstructures.     

Template-free synthesis of mesoporous γ-alumina with tunable structural properties

Mesoporous γ-Al₂O₃ (MA) with agglomerated nanoparticles was successfully synthesized by using aluminum sulfate as inorganic Al resource, and hexamethylene tetramine (HMTA) as precipitant without using any surfactants, via a hydrothermal method. All the experimental processes experienced the hydrolysis, precipitation and calcination steps. The structural and morphological properties of uncalcined and calcined samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetry differential thermal gravity (TG-DTG) and N₂ adsorption–desorption. The bulk density of the sample is 0.682 cm³  g⁻¹, and the specific surface area is 273.302 m² g⁻¹. The pore diameters (7.1 nm and 9.7 nm) indicate that a typical bimodal mesoporous structure was formed within MA. In order to tune the structural properties of MA, various kinds of inorganic aluminum sources and precipitating agents were employed to carry out contrast experiments, which leaded to regular variations in the specific surface area (200.898–273.302 m² g⁻¹), pore volume (0.121–1.327 cm³ g⁻¹) and pore size (3.7–35.9 nm). At the same time, the experimental results also demonstrated that the various kinds of Al resources and precipitants had no effects on the crystal structure of MA. However, the morphologies of samples, such as nanoparticles, short fibers, flower-like and block-shaped, can be controlled effectively. The present study provides a simple and effective approach for preparing MA, and the structural properties of MA can be controlled precisely by carefully choosing aluminum sources and precipitants. The approach of this work not only allows us to investigate the growth mechanism of the final product, but also reduces cost and the environmental pollution effectively than other template methods.     

Structure and magnetic properties of Co3O4/SiO2 nanocomposite synthesized using combustion assisted sol-gel method

This paper reports on novel cobalt oxide nanoparticles (NPs) embedded in an amorphous silica (SiO₂) matrix, synthesized using a modified sol-gel method. SEM and TEM images show as-synthesized particles to aggregate in the shape of spheres and less than 5 nm in size, while XRD and SAED analysis both point to well crystallized cubic spinel cobalt oxide phase with an average crystallite size of about 4.6 nm. Raman analysis confirms the formation of cobalt (III) oxide (Co₃O₄) NPs. As-synthesized Co₃O₄ single-nanocrystallite has magnetic properties that correlate with finite size effects and uncompensated surface spins. Temperature dependence of ZFC-FC magnetization curves reveals a sharp peak around 10 K which corresponds to the blocking temperature. A Curie-Weiss behavior of magnetization above 25 K shows lower Néel temperature of the sample compared with its bulk counterpart T_N=40 K (possibly due to crystal defects and nano-dimensionality of the particles). The magnetic measurements exhibit high magnetization at low temperatures (M_S=54.3 emu/g) which can be associated with random canting of the particles’ surface spins and uncompensated spins in the core which tends to interact ferromagnetically at low temperatures. The initial magnetization curve falls out from the hysteresis loop at 5 K, which could be also the effect of surface spins.     

Microstructure and high temperature 4-point bending creep of sol–gel derived mullite ceramics

Four-point bending creep behavior of mullite ceramics with monomodal and bimodal distribution of grain sizes was studied in the temperature range of 1320–1400 °C under the stresses between 40 and 160 MPa. Mullite ceramic with bimodal grain size distribution was prepared using aluminum nitrate nonahydrate as alumina precursor. When γ-Al₂O₃ or boehmite were used as alumina precursors, mullite grains are equiaxial with mean particle size of 0.6 μm for the former and 1.3 μm for the latter alumina precursor. The highest creep rate exhibited the sample with monomodal morphology and grains in size of 0.6 μm, which is about one order of magnitude greater than that for the monomodal morphology but with grains in size of 1.3 μm. The highest activation energy for creep (Q = 742 ± 33 kJ/mol) exhibits mullite with equiaxial grains of 1.3 μm, whereas for sample with smaller equiaxial grains the activation energy is much smaller and similar to mullite ceramics with bimodal grain morphology. Intergranular fracture is predominant near the tension surface, while transgranular more planar fracture is predominant near the compression surface zone.     

Spark plasma sintering of ultra-porous γ-Al2O3

Nanocrystalline gamma alumina (γ-Al₂O₃) powder with a crystallite size of ~10 nm was synthesized by oxidation of high purity aluminium plate in a humid atmosphere followed by annealing in air. Spark plasma sintering (SPS) at different sintering parameters (temperature, dwell time, heating rate, pressure) were studied for this highly porous γ-Al₂O₃ in correlation with the evolution in microstructure and density of the ceramics. SPS sintering cycles using different heating rates were carried out at 1050–1550 °C with dwell times of 3 min and 20 min under uniaxial pressure of 80 MPa. Alumina sintered at 1550 °C for 20 min reached 99% of the theoretical density and average grain size of 8.5 µm. Significant grain growth was observed in ceramics sintered at temperatures above 1250 °C.     

Effect of polymer concentration on porosity and pore size characteristics of alumina membrane substrates prepared by gelcasting

The effect of urea–formaldehyde (UF) polymer concentration on porosity and average pore size of alumina membrane substrates prepared by gelcasting has been studied. The soluble UF oligomers formed in the initial stages of polymerization act as steric stabilizer for alumina particles in the suspension. The porosity and average pore size of the substrate samples decreased with both the decrease of amount of polymer in the gelcast body and the increase of sintering temperature. Membrane substrates obtained by sintering of gelcast bodies containing UF polymer concentrations from 24.3 to 15.6 wt% at temperatures from 1250 to 1450 °C showed porosity and average pore size of 62.5–27 vol% and 0.43–0.20 μm, respectively. The membrane substrates prepared by the gelcasting method had narrow pore size distribution.